Process of making artificial resins



' UNITED STATES.

PATENT orrlcs.

OA BLETON ELLIS, OF MONTGLAIR, AN D HARRY M. WEBER, OF IBLOOEFIELID, NEW

JERSEY, ASSIGNORS TO ELLIS-FQSTER COMPANY,

A. CORPORATION or NEW Specification 01 Letters Patent. Patented June 141921.

JERSEY.

PROCESS OF MAKING ARTIFICIAL RESINS.

No Drawing.

To all whom it may concern:

Be it known that we, CARLETON' Exam and:

HARRY M. WEBER, citizens of the United 1) States, and residents, resectively, of Montclair, in the count of ssex andstate of New Jersey, andloomfield in the county of Essex and State of New jersey, have inventedcertain new and useful Improvements in Processes of Making ArtificialResins, of which the following is a specification.

This invention relates to a process of making certain resinoussubstances which have low acid numbers and which may be used in Forexample ordinary rosin may be treated with quick lime to form a resinateof lime and this treated with glycerin to yield the composite of lowacid number. In one case 300 parts of ordinary rosin was treated with 12parts by weight of quicklime, the mixture being heated at 290 C. for ahalf hour. 40 parts of glycerin was then added and the temperature ofthe resinate held between 270290 C. for a half hour with agitation whena product having an acid number of 9 was obtained. The product had asatisfactory degree of hardness.

. Likewise calcium cyanamid may be used for reaction with the resin inthe first instance or for making a hardened product without subsequenttreatment with glycerin. For example 200 parts by weight of ordinaryrosin was treated with 10 parts of calcium cyanamid for a half hour andthen treated with 16 parts of glycerin for a half hour at a temperaturebetween 270290 C. This afforded a product having the very desirable acidnumber of 5. In a similar manner magnesia, barium oxid or other base maybe used as a means of forming a resinate which may then be reacted uponwith glycerin, lycol or other reagent of this character to orm theresinous complex desired.

Application as October 2, 1920. Serial No. 414,279.

1 4 I A product may be obtained reacting on IOSlIl or other resins withchlorhydrin which roduct has a reduced acid number. For example 100parts by weight of rosin was heated with 50 parts of chlorhydrin at thebolllng point of the mixture the heating belng carried on for two hoursunder a reflux condenser. The chlorhydrin wasobtained by treatlng oilgas with hypochlorous acid and was a mlxture of the ethylene andpropylene chlorhydrins. This treatment reduced the original acid numberfrom its original point of 161 down to 113. On boillng for a furtherperiod of 8 hours the acid number dropped to 19. This produced a softresin having an excess of chlorhydrin and the product was distilled toremove the excess of the reagent. Distillate came over between 120-140C. tion the acid number of the resin was 57.

. The resin obtained in this manner was easily soluble in alcohol andwas light in color.

In carrying out this method on the resinate for example lime resinateprepared as above may be boiled with the chlorhydrin to bring aboutsuitable reaction.

In making. the esters of fossil resins such for example as that ofpontianak, manila and particularly congo resin or gum the fossil resinmay first be treated with lime or other basic material capable offorming a resinate and the latter then heated with glycerin or glycol,etc., to produce the complex desired. A more desirable complex howeveris obtained by reacting upon copal and ordinary rosin, either inadmixture as such or in the form of their resinates with glycerin. Forexample 4 or 5 parts of congo gum with 1 or 2 parts of ordinary rosinare melted and are heated at about 300310 C. in order to convert thecongo gum into a soluble fusible product. Glycerin is then introducedand the reaction allowed to progress until the acid number of thecomposition has fallen to approximately 10.

, When fossil resins are heated to render them suitable for varnishpurposes they do not fuse readily but have to be heated to quite a hightemperature for a considerable eriod in order to obtain a fusibleproduct. or example congo gum when heated and stirred will gather into agummy mass which is extremely diflicult to manipulate. If however, thecongo gum is heated with 10% or After this distilla-,

more of ordinary rosin the heating goes on smoothly and agitation may beused advantageously. Moreover the rosin itself is hardened b the heatingand more or less blended with e congo m so that a mixture of the fossilresin mi the ordinary rosin is obtained which is of a very intimatecharacter and in fact possibly there may'have been some combinationbetween the two resins during the heating operation. In any event thiscombination, mixture or compound when heated to the point that it isreadily wit fusible is in condition for treatment glycerin to form thecomplex desired,

namely'the congo resin and rosin compound of lycerin, or on the otherhand the congo am? rosin, lime resinate or other resinate com lex withglycerin.

The formation of this product may be carried out at .atmosphericpressure in a closed kettle fitted with an a 'tator. The kettle andagitator are pr'eferab y coated with glass or enamel so that the acidresins do not come in contact with metals which would discolor them. Avent is provided for the elimination of steamiormed during the reaction.=Preferablfy this takes the form of an air condenser 0 such length thatglycerin which may be volatized is returned to V the kettle. Thetemperature of the'operation is generally in the nelghborhood of 290.G.but may vary betweenf270-290 C. or even more under some conditions.

In carrying out the reaction in glass,

A modificatiiiii of the foregoing method of forming the complex is thatof first preparing. a bath of molten rosin, ordina rosin or colophonybeingused; this is pre erably prepared in a vessel covered so as toexclude the air and having a vent for the escape of vapors but soarranged that the air does not readily come in contact with the rosinsurface. he bath of rosin is heated to around 300 C. and congo resin isadded gradually with stirring to form a solution of the congo in therosin. More and more congo gum may be added until finally a mixture ofresins containing more 'of the fossil resin than ordinary resin isobtained.

without the formation at any time of coaguham or separated fossil resin.In this way a particularly light colored resin combinacerin producinsuited to form a suitable complex wi glycerin.

tion may be secured. which is eminently 11 place of rosin it is possiblealso to use previously run congo gum or other run fossil resin, that isone which has'been heated to render it fusible and suited for use in thepreparation'of varnishes. In running fossil resins of this sort care istaken to distil off all oil produced during the process so that noso-called, copal oil 18 present, it being desired to heat the fossilresin with a I fusible solid resin in order to bring about fusibility ofthe original fossil resin under. these conditions and to promotereaction as far as possible between two resins. Henceall oily fluxingmaterial is pilreferabl avoided. In like manner the finis ed rod uct maybe introduced into the fusing ettle and the fossil resin rejectedinto amolten bath of the latter. 'Fhus the reaction roduct of congo gum,ordinary rosin an glyafusible product may be used as the mo ten bath orfluxing agent to dissolve and fuse additional quantities of congo gum. 1

This is advanta eous especially when limited kettle facilities areavailable as after the completion of the operation with glycerin thekettle may be emptied of say twothirds or three-fourths of the quantityof material prwent and fresh fossil resin such as congo gum and otherresin desired introduced to bring the contents of the kettle up to therequisite charge. Thus the operation may be carried on continuously withsimple inexpensive equipment.

In discharging the finished complex in its highly heated moltencondition care should i be taken to avoid contact with air or oxygen.The cooling should take place in an atmosphere practically free fromoxygen in order to secure the'lightest colored product obtainable'. Forthis reason it is best to run the material into a container filled withinert gas such as carbon dioxid or nitrogen and allow the temperature tofall to between.

100-150 C. before the resin is actually brought into contact with theair. Thus the batch may be discharged through a cooling coil or pipearranged todeliver the product to a receiver at a temperature of about100 C. at which temperature practically no discoloration on exposure tothe air will occur. In some cases benzyl alcohol may be used eitheralone or with glycerin or glycol to form a different type of resinouscomplex. To recapitulate the invention involved herein comprises thetreatment of ordinary rosin or fusible resin of, the nature of colophonor fossil resin such as pontianak, mani a, congo, kauri and other copalswith a reagent capable of reducing the acid numher to a substantialextent and also one whichpreferably simultaneously hardens the resin inconsiderable degree and relates in part to the formation of lime orother resinates and subsequent treatment of these with glycerin orsimilar reagent to form complexes in which the resin is combined withthe lime or other base and with the glycerin, glycol or other similaragent and further relates to the co-treatment of a fossil resin and afusible resinous body whereby from the infusible fossil resin a fusibleresinous mixture is obtained without fluxing agent and the treatment ofsuch resinous mixture or composite with glycerin, glycol or similarreagent to produce highly complex resinous substances having relatively.

low acid numbers and being capable of being fused and dissolved inlinseed and other oils, turpentine and the like to form varnishes orgrinding varnishes with basic pigments which do not harden or liver inan objectionable manner. The invention further comprises, in certainphases at least, other details of procedure as noted above and alsocomprises the product of such process, namely the glycerin reactionpro'ductof a mixture of a fossil resin and a fusible resin and theglycerin reaction product of a mixture of resinates of lime or otherbases.

In heating an infusible copal resin with a fusible solid resin such asordinary rosin as stated, a temperature of approximately 300 C. ispreferable and in carrying out this heatin the kettle, while referablycovered is preferably also vented so as to allow 0 the ready escape ofthe copal oil which is formed or any oils that may be produced bydecomposition of the rosin so that the fusible resinous product obtainedby this heat treatment is substantially free from any liquid oilymaterial especially hydrocarbons which might tend to reduce the meltingpoint of the product and render it less adapted for final reaction withthe glycerin, glycol or similar reagent.

What we claim is 1. The process of forming a resinous composition whichcomprises heating an infusible fossil resin in the presence of a fusiblesolid resin with glycerin whereby a complex of low acid number isproduced.

2. The process of making a resinous composition which comprises heatinga copal resin in the presence of a fusible solid resin, in expelling anycopal oil formed as rapidly as produced and in treating the fusibleresinous compositionobtained thereby with glycerin to produce a complexof low acid number.

3. The process of producing a resinous composition which comprisesdissolving congo um in molten rosin at approximately 300 heatin at thistemperature and permitting copa oil to escape and finally reacting uponthe composition substantially freed of all oily material with a quantityof glycerin at approximately atmospheric temperature with agitation;wherebyaresinous complex of low acid number is obtained.

4. A resinous product comprising the reaction products of fusible copalresin, ordinary rosin and glycerin.

5. A resinous product comprising the product of reaction of congo gum,ordinary rosin and glycerin, said composition being substantially freefrom copal oil and rosin '1. 01 GARLETON ELLIS.

HARRY M. WEBER.

